铜片-纳米金表面增强拉曼基底的制备及检测应用
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摘要
SERS因灵敏度高、制样简便等优势,在食品安全、环境监测等方面应用潜力巨大.SERS技术实现商业化的关键在于如何低价、简便、快速得到重现性良好、可多次循环使用的SERS基底.针对这一难题,开发了一种利用廉价铜片原位还原制备SERS基底的简便新方法.经硝酸处理的铜片原位还原氯金酸,生成的纳米金则覆盖于铜片表面.经检测,所制得的铜片-纳米金基底(Cu F-Au NPs)表面粗糙度均一.利用该基底检测不同浓度的罗丹明B(RHb),实验结果显示浓度和SERS峰强度满足关系y=1 492x+12 435,R~2=0.995,检测下限达到1×10~(-8),mol/L,表明该Cu F-AuNPs基底可用于目标物的定性及定量检测.选取1×10~(-6),mol/L的RHb样品4次循环检测,结果表明该工艺条件下制备得到的CuF-AuNPs基底具有良好的重现性.
Based on its high-sensitivity and simple sample preparation,surface-enhanced Raman scattering(SERS)has a wide application in food safety and environmental survey.To commercialize SERS,the key point is to develop a low-cost,simple,and convenient method to obtain a recyclable and high-quality SERS substrate.Therefore,a novel and cheap copper foil-gold nanoparticles(Cu F-Au NPs)SERS substrate was fabricated by in-situ reduction of AuNPs on the rough surface of copper foil using nitric acid.The effect of nitric acid concentration on the surface roughness of copper foil and the effect of reduction time on the merits of the CuF-AuNPs substrate were investigated.The Raman scattering signal of Rhodamine B(RHb)under different concentrations was detected on CuFAu NPs.A good linear(y=1,492,x+12,435,R~2=0.995)relationship was obtained between the characteristic peak intensity of RHb and its logarithmic concentration.The detection limit reached 1×10~(-8),mol/L,indicating that the CuF-AuNPs substrate exhibited remarkable potential and good sensitivity in qualitative and quantitative detection.The results of four-time-cycle detection of RHb under 1×10~(-6),mol/L exhibited a negligible difference,demonstrating a good reproducibility of CuF-AuNPs for Raman scattering detection.
Based on its high-sensitivity and simple sample preparation,surface-enhanced Raman scattering(SERS)has a wide application in food safety and environmental survey.To commercialize SERS,the key point is to develop a low-cost,simple,and convenient method to obtain a recyclable and high-quality SERS substrate.Therefore,a novel and cheap copper foil-gold nanoparticles(Cu F-Au NPs)SERS substrate was fabricated by in-situ reduction of AuNPs on the rough surface of copper foil using nitric acid.The effect of nitric acid concentration on the surface roughness of copper foil and the effect of reduction time on the merits of the CuF-AuNPs substrate were investigated.The Raman scattering signal of Rhodamine B(RHb)under different concentrations was detected on CuFAu NPs.A good linear(y=1,492,x+12,435,R~2=0.995)relationship was obtained between the characteristic peak intensity of RHb and its logarithmic concentration.The detection limit reached 1×10~(-8),mol/L,indicating that the CuF-AuNPs substrate exhibited remarkable potential and good sensitivity in qualitative and quantitative detection.The results of four-time-cycle detection of RHb under 1×10~(-6),mol/L exhibited a negligible difference,demonstrating a good reproducibility of CuF-AuNPs for Raman scattering detection.
引文
[1]Stiles P L,Dieringer J A,Shah N C,et al.Surfaceenhanced Raman spectroscopy[J].Annual Review of Analytical Chemistry,2008,1:601-626.
[2]Deckert V.Tip-enhanced raman spectroscopy[J].Journal of Raman Spectroscopy,2009,40(10):1336-1337.
[3]Hirschfeld T,Chase B.FT-Raman spectroscopy:Development and justification[J].Applied Spectroscopy,1986,40(2):133-137.
[4]Pisarek M,Roguska A,Kudelski A,et al.The role of Ag particles deposited on TiO2 or Al2O3 self-organized nanoporous layers in their behavior as SERS-active and biomedical substrates[J].Materials Chemistry and Physics,2013,139(1):55-65.
[5]Han X X,Chen L,Kuhlmann U,et al.Magnetic titanium dioxide nanocomposites for surface-enhanced resonance Raman spectroscopic determination and degradation of Toxic anilines and phenols[J].Angewandte Chemie International Edition,2014,53(9):2481-2484.
[6]Qian X,Peng X-H,Ansari D O,et al.In vivo tumor targeting and spectroscopic detection with surfaceenhanced Raman nanoparticle tags[J].Nature Biotechnology,2008,26(1):83-90.
[7]唐晓萍,张孝芳,齐小花,等.表面增强拉曼散射光谱快速检测纺织品还原液中联苯胺[J].分析化学,2015,43(8):1224-1230.Tang Xiaoping,Zhang Xiaofang,Qi Xiaohua,et al.Rapid detection of benzidine in reducing solution of textiles by surface-enhanced raman scattering spectroscopy[J].Chinese Journal of Analytical Chemistry,2015,43(8):1224-1230(in Chinese).
[8]Kubackova J,Fabriciova G,Miskovsky P,et al.Sensitive surface-enhanced Raman spectroscopy(SERS)detection of organochlorine pesticides by alkyl dithiolfunctionalized metal nanoparticles-induced plasmonic hot spots[J].Analytical Chemistry,2015,87(1):663-669.
[9]Cao Q,Liu X,Yuan K,et al.Gold nanoparticles decorated Ag(Cl,Br)micro-necklaces for efficient and stable SERS detection and visible-light photocatalytic degradation of Sudan I[J].Applied Catalysis B:Environmental,2017,201:607-616.
[10]黄梅英,李攻科,胡玉玲.表面增强拉曼光谱法定量检测食品中香豆素[J].分析化学,2015,43(8):1218-1223.Huang Meiying,Li Gongke,Hu Yuling.Quantitative dfetermination of coumarin in food by surface-enhanced raman spectroscopy[J].Chinese Journal of Analytical Chemistry,2015,43(8):1218-1223(in Chinese).
[11]赵蕊池,王培龙,石雷,等.自组装有序纳米银线表面增强拉曼光谱检测牛奶中三聚氰胺[J].分析化学,2017,45(1):75-82.Zhao Ruichi,Wang Peilong,Shi Lei,et al.Determination of melamine in milk by surface enhanced Raman scattering technique based on self-assemble[J].Chinese Journal of Analytical Chemistry,2017,45(1):75-82(in Chinese).
[12]Schlucker S.Surface-enhanced Raman spectroscopy:Concepts and chemical applications[J].Angewandte Chemie International Edition,2014,53(19):4756-4795.
[13]Frens G.Controlled nucleation for the regulation of the particle size in monodisperse gold suspensions[J].Nature,1973,241(105):20-22.
[14]Lee P,Meisel D.Adsorption and surface-enhanced Raman of dyes on silver and gold sols[J].Journal of Physical Chemistry,1982,86(17):3391-3395.
[15]Huang X,El-Sayed I H,Qian W,et al.Cancer cell imaging and photothermal therapy in the near-infrared region by using gold nanorods[J].Journal of the American Chemical Society,2006,128(6):2115-2120.
[16]Garcia-Leis A,Garcia-Ramos J V,Sanchez-Cortes S.Silver nanostars with high SERS performance[J].The Journal of Physical Chemistry C,2013,117(15):7791-7795.
[17]Jena B K,Mishra B,Bohidar S.Synthesis of branched Ag nanoflowers based on a bioinspired technique:Their surface enhanced Raman scattering and antibacterial activity[J].The Journal of Physical Chemistry C,2009,113(33):14753-14758.
[18]Lu H,Zhu L,Zhang C,et al.Highly uniform SERS-active microchannel on hydrophobic PDMS:A balance of high reproducibility and sensitivity for detection of proteins[J].RSC Advances,2017,7(15):8771-8778.
[19]Su J,Wang D,N?rbel L,et al.Multicolor gold-silver nano-mushrooms as ready-to-use SERS probes for ultrasensitive and multiplex DNA/miRNA detection[J].Analytical Chemistry,2017,89(4):2531-2538.
[20]Ma S,Li Q,Yin Y,et al.Interference-free surfaceenhanced Raman scattering tags for single-cell molecular imaging with a high signal-to-background ratio[J].Small,2017,13(15):1603340.
[21]Cottat M,Lidgi-Guigui N,Tijunelyte I,et al.Soft UVnanoimprint lithography-designed highly sensitive substrates for SERS detection[J].Nanoscale Research Letters,2014,9(1):623-629.
[22]Dai Z,Mei F,Xiao X,et al.“Rings of saturn-like”nanoarrays with high number density of hot spots for surface-enhanced Raman scattering[J].Applied Physics Letters,2014,105(3):033515.
[23]Liu Z,Yan Z,Jia L,et al.Gold nanoparticle decorated electrospun nanofibers:A 3D reproducible and sensitive SERS substrate[J].Applied Surface Science,2017,403:29-34.
[24]Song G,Zhou H,Gu J,et al.Tumor marker detection using surface enhanced Raman spectroscopy on 3D Au butterfly wings[J].Journal of Materials Chemistry B,2017,5(8):1594-1600.
[25]Tanahashi I,Harada Y.Silver nanoparticles deposited on TiO2-coated cicada and butterfly wings as naturally inspired SERS substrates[J].Journal of Materials Chemistry C,2015,3(22):5721-5726.
[2]Deckert V.Tip-enhanced raman spectroscopy[J].Journal of Raman Spectroscopy,2009,40(10):1336-1337.
[3]Hirschfeld T,Chase B.FT-Raman spectroscopy:Development and justification[J].Applied Spectroscopy,1986,40(2):133-137.
[4]Pisarek M,Roguska A,Kudelski A,et al.The role of Ag particles deposited on TiO2 or Al2O3 self-organized nanoporous layers in their behavior as SERS-active and biomedical substrates[J].Materials Chemistry and Physics,2013,139(1):55-65.
[5]Han X X,Chen L,Kuhlmann U,et al.Magnetic titanium dioxide nanocomposites for surface-enhanced resonance Raman spectroscopic determination and degradation of Toxic anilines and phenols[J].Angewandte Chemie International Edition,2014,53(9):2481-2484.
[6]Qian X,Peng X-H,Ansari D O,et al.In vivo tumor targeting and spectroscopic detection with surfaceenhanced Raman nanoparticle tags[J].Nature Biotechnology,2008,26(1):83-90.
[7]唐晓萍,张孝芳,齐小花,等.表面增强拉曼散射光谱快速检测纺织品还原液中联苯胺[J].分析化学,2015,43(8):1224-1230.Tang Xiaoping,Zhang Xiaofang,Qi Xiaohua,et al.Rapid detection of benzidine in reducing solution of textiles by surface-enhanced raman scattering spectroscopy[J].Chinese Journal of Analytical Chemistry,2015,43(8):1224-1230(in Chinese).
[8]Kubackova J,Fabriciova G,Miskovsky P,et al.Sensitive surface-enhanced Raman spectroscopy(SERS)detection of organochlorine pesticides by alkyl dithiolfunctionalized metal nanoparticles-induced plasmonic hot spots[J].Analytical Chemistry,2015,87(1):663-669.
[9]Cao Q,Liu X,Yuan K,et al.Gold nanoparticles decorated Ag(Cl,Br)micro-necklaces for efficient and stable SERS detection and visible-light photocatalytic degradation of Sudan I[J].Applied Catalysis B:Environmental,2017,201:607-616.
[10]黄梅英,李攻科,胡玉玲.表面增强拉曼光谱法定量检测食品中香豆素[J].分析化学,2015,43(8):1218-1223.Huang Meiying,Li Gongke,Hu Yuling.Quantitative dfetermination of coumarin in food by surface-enhanced raman spectroscopy[J].Chinese Journal of Analytical Chemistry,2015,43(8):1218-1223(in Chinese).
[11]赵蕊池,王培龙,石雷,等.自组装有序纳米银线表面增强拉曼光谱检测牛奶中三聚氰胺[J].分析化学,2017,45(1):75-82.Zhao Ruichi,Wang Peilong,Shi Lei,et al.Determination of melamine in milk by surface enhanced Raman scattering technique based on self-assemble[J].Chinese Journal of Analytical Chemistry,2017,45(1):75-82(in Chinese).
[12]Schlucker S.Surface-enhanced Raman spectroscopy:Concepts and chemical applications[J].Angewandte Chemie International Edition,2014,53(19):4756-4795.
[13]Frens G.Controlled nucleation for the regulation of the particle size in monodisperse gold suspensions[J].Nature,1973,241(105):20-22.
[14]Lee P,Meisel D.Adsorption and surface-enhanced Raman of dyes on silver and gold sols[J].Journal of Physical Chemistry,1982,86(17):3391-3395.
[15]Huang X,El-Sayed I H,Qian W,et al.Cancer cell imaging and photothermal therapy in the near-infrared region by using gold nanorods[J].Journal of the American Chemical Society,2006,128(6):2115-2120.
[16]Garcia-Leis A,Garcia-Ramos J V,Sanchez-Cortes S.Silver nanostars with high SERS performance[J].The Journal of Physical Chemistry C,2013,117(15):7791-7795.
[17]Jena B K,Mishra B,Bohidar S.Synthesis of branched Ag nanoflowers based on a bioinspired technique:Their surface enhanced Raman scattering and antibacterial activity[J].The Journal of Physical Chemistry C,2009,113(33):14753-14758.
[18]Lu H,Zhu L,Zhang C,et al.Highly uniform SERS-active microchannel on hydrophobic PDMS:A balance of high reproducibility and sensitivity for detection of proteins[J].RSC Advances,2017,7(15):8771-8778.
[19]Su J,Wang D,N?rbel L,et al.Multicolor gold-silver nano-mushrooms as ready-to-use SERS probes for ultrasensitive and multiplex DNA/miRNA detection[J].Analytical Chemistry,2017,89(4):2531-2538.
[20]Ma S,Li Q,Yin Y,et al.Interference-free surfaceenhanced Raman scattering tags for single-cell molecular imaging with a high signal-to-background ratio[J].Small,2017,13(15):1603340.
[21]Cottat M,Lidgi-Guigui N,Tijunelyte I,et al.Soft UVnanoimprint lithography-designed highly sensitive substrates for SERS detection[J].Nanoscale Research Letters,2014,9(1):623-629.
[22]Dai Z,Mei F,Xiao X,et al.“Rings of saturn-like”nanoarrays with high number density of hot spots for surface-enhanced Raman scattering[J].Applied Physics Letters,2014,105(3):033515.
[23]Liu Z,Yan Z,Jia L,et al.Gold nanoparticle decorated electrospun nanofibers:A 3D reproducible and sensitive SERS substrate[J].Applied Surface Science,2017,403:29-34.
[24]Song G,Zhou H,Gu J,et al.Tumor marker detection using surface enhanced Raman spectroscopy on 3D Au butterfly wings[J].Journal of Materials Chemistry B,2017,5(8):1594-1600.
[25]Tanahashi I,Harada Y.Silver nanoparticles deposited on TiO2-coated cicada and butterfly wings as naturally inspired SERS substrates[J].Journal of Materials Chemistry C,2015,3(22):5721-5726.